Assembling Inorganic Nanocrystal Gels.

Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network-structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advantages in terms of gel stability, reversibility, or tunability and presents new opportunities for the design of reconfigurable materials and fueled assemblies.

Effective Hard-Sphere Repulsions between Oleate-Capped Colloidal Metal Oxide Nanocrystals.

Nanocrystal interactions in solvent influence colloidal stability and dictate self-assembly outcomes. Small-angle X-ray scattering is used to study how dilute oleate-capped In2O3 nanocrystals with 7-19 nm core diameters interact when dispersed in a series of nonpolar solvents. Osmotic second virial coefficient analysis finds toluene-dispersed nanocrystals in this size range interact like effective hard spheres with diameters comprising the inorganic core and a ligand-solvent corona with a core-size independent thickness. Hard-sphere-like structure factors are similarly observed for nanocrystals with a 9.7 nm core diameter dispersed in all the solvents investigated. Nanocrystal hydrodynamic diameters from dynamic light scattering measurements correlate with thermodynamic diameters obtained from the osmotic second virial coefficient analysis for all samples. The ability to prepare nanoscale building blocks of different sizes, and dispersed in a variety of solvents, with effective hard-sphere repulsions provides a foundation for assembly, where secondary linking or depletant molecules can be deliberately added to customize interactions to form superstructures such as gel networks or superlattices.

Aqueous transfer of colloidal metal oxide nanocrystals via base-driven ligand exchange.

A general method is developed for removal of native nonpolar oleate ligands from colloidal metal oxide nanocrystals of varying morphologies and compositions. Ligand stripping occurs by phase transfer into potassium hydroxide solution, yielding stable aqueous dispersions with little nanocrystal aggregation and without significant changes to the nanomaterials' physical or chemical properties. This method enables facile fabrication of conductive films of ligand-free nanocrystals.

Pyridinium-Functionalized Pyromellitic Diimides with Stabilized Radical Anion States.

In this work, we report the stabilization of the reduced states of pyromellitic diimide by charge-balancing the imide radical anions with cationic pyridinium groups attached to the aromatic core. This structural modification is confirmed by single-crystal X-ray diffraction analysis. Characterization by (spectro)electrochemical experiments and computations reveal that the addition of cationic groups to an already electron-deficient ring system results in up to +0.57 V shifts in reduction potentials, largely as a consequence of charge screening and lowest unoccupied molecular orbital-lowering effects. This formal charge-balancing approach to stabilizing the reduced states of electron-deficient pyromellitic diimides will facilitate their incorporation into spin-based optoelectronic materials and devices.